Boric anhydride solutions and their use as hardeners of resols

ABSTRACT

Concentrated boric anhydride solutions containing more than 5% of boric anhydride in an organic solvent selected from mono or polyalcohols, trialkylborate and/or dialkylacetal when the solvent also contains an acid selected from sulfuric acid and/or aromatic acids. These solutions are used as hardeners of formo-phenolic resols, more particularly for the manufacture of laminates comprising glass fibers and formo-phenolic resols.

This is a division, of application Ser. No. 49,009 filed June 15, 1979, now U.S. Pat. No. 4,272,403, issued June 9, 1981.

BACKGROUND OF THE INVENTION

The present invention is related to boric anhydride solutions and the use of these solutions as hardeners of resols.

Boric anhydride (B₂ O₃) is a product which has numerous uses including use as a fire-proofing agent, as a dehydrating agent, as a catalyst or as a co-catalyst. The product is in a solid form (particles, granular form, powders) and no solvent is known in which boric anhydride has an appreciable solubility at least equal to 5 percent by weight. In order to facilitate handling and dispersion of boric acid in reaction mixtures it is desired to use boric anhydride in liquid form such as in the form of solutions, preferably concentrated solutions. This is one object of the present invention.

SUMMARY OF THE INVENTION

It has been found that anhydrous solutions having high concentrations of boric anhydride are obtained when boric anhydride is added to one or more organic solvents in the presence of an acid chosen among concentrated sulfuric acid and aromatic sulfonic acids. It has been found that boric anhydride, which is only slightly soluble either in an acid or in a solvent, dissolves in noticeably increased quantities in organic solvents or mixtures of solvents in the presence of at least one acid.

The obtained solutions are anhydrous and most often clear. Sometimes owing to the presence of water a slight hydrolysis of anhydride takes place and the obtained solution is slightly turbid.

The concentration in boric anhydride of the obtained solutions is variable and depends on the solvent or on the solvents and on the acid which are used. However limpid solutions containing up to 40 percent by weight of boric anhydride are easily obtained.

The organic solvents used according to the present invention are mono or polyalcohols, trialkylborates, or dialkylacetals of formol. Suitable organic solvents are for example, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, trimethyl borate [B (OCH₃)₃ ] or methylal [CH₂ (OCH₃)₂ ] Preferably the mixtures of trimethyl borate and methanol or of trimethyl borate and methylal are used. When using these mixtures the dissolution speed of boric anhydride is increased by about ten times. Moreover these mixtures of solvents are easy to find and are therefore less expensive. This is for example the case for the mixture of trimethylborate and methanol.

The presence of an acid even used in slight amounts increases the solubility of boric anhydride in the solvent. The solubility of boric anhydride increases with the added amount of acid. In practice a quantity of acid equal to at least 5 percent by weight in comparison with boric anhydride solution and at most 70 percent by weight is suitable. When amounts of acid inferior to 5 percent by weight are used, the solutions obtained contain large amounts of solvents which have to be eliminated when the solutions are used as catalysts of resols. When solutions contain more than 70 percent by weight of acid the obtained catalytic system is too efficient. Generally according to the present invention solutions containing at least 10 percent by weight and preferably 15 to 50 percent by weight of acid are used.

Suitable aromatic sulfonic acids are for example para-toluene sulfonic acid, benzene sulfonic acid and xylene sulfonic acid.

The mixtures of the present invention containing at least one organic solvent such as described hereabove and at least one acid selected from sulfuric acid and aromatic sulfonic acids have in regard to boric anhydride a solvent power which is superior to the solvent power of the constituents taken alone, (the solvent power is defined as being the maximum concentration of boric anhydride in the solution).

The solutions of the present invention are prepared according to known ways, the different constituents being added in any order except for sulfuric acid for which the usual rules are to be followed. The mixture is achieved with stirring at room temperature.

Another object of the present invention is the use of the obtained solutions as hardeners of formo-phenolic resols.

U.S. Pat No. 4,123,414 relates to a process for the manufacture of laminates constituted by glass fibers and formo-phenolic resols according to which the formo-phenolic resol, hardener, glass fibers and a dehydrating agent, in particular, boric anhydride, are simultaneously sprayed on a mold.

This process has two drawbacks: it is necessary to achieve a simultaneous spraying of products in the liquid form and of products in the solid form, and to determine in a precise way the amount of one of the two used solid products (B₂ O₃); the second drawback being that molding has to be carried out by the spraying of the constituents technique.

By using solutions of the present invention the difficulties described hereabove are resolved. The hardener (sulfuric acid and/or aromatic sulfonic acid) used contains boric anhydride in a well defined proportion and being in a liquid form is easy to use. Furthermore it is possible to prepare the laminates by injection or by molding with a press according to the hot or cold technique. The solutions according to the present invention are suitable for the hardening of resols. The skilled art worker will choose solutions with a solvent which is compatible with the aqueous solution of resol.

The obtained solutions according to the present invention are suitable for the known resols: either the resols obtained only by condensing formol and phenol in the presence of an alkaline catalyst or a resol containing also additive compounds, such as surfactants or plasticizers. The solutions obtained according to the present invention can be used as the sole catalysts for the resols. In such a case it is preferable that the acid concentration be at least 15 percent by weight, since for weaker concentrations of acid, large amounts of solvents are present. However in addition to solutions described in the present invention it is possible to use other catalysts which are known. The boric anhydride concentration in the solutions of the present invention is preferably comprised between 10 and 35 percent by weight based on the weight of solution.

The following examples are given by way of illustration. Quantities are given in parts by weight.

EXAMPLE 1

Solutions were prepared by adding with stirring powdery boric anhydride and varying acids and solvents. Table 1 gives boric anhydride solubility.

                  TABLE 1                                                          ______________________________________                                                                  BORIC                                                                          ANHYDRIDE                                                COMPOUND              SOLUBILITY                                            ______________________________________                                         Sulfuric acid 95 percent by weight                                                                      2.25%                                                   Methylal               1.40%                                                   Methanol               2,00%                                                   Ethanol                2.60%                                                 Dipropylene glycol       0.80%                                                   Trimethyl borate       3.50%                                                 Mixture         trimethyl borate                                                                           70%                                                (in weight)     methanol    30%    4,50%                                       Mixture         trimethyl borate                                                                           70%                                                (in weight)     isopropanol 30%    2.00%                                       Mixture         trimethyl borate                                                                           70%                                                (in weight)     butanol     30%    1.50%                                       ______________________________________                                    

EXAMPLE 2

Example 1 was repeated by using mixtures constituted with acid and solvents.

Table 2 gives boric anhydride solubility at room temperature.

                  TABLE 2                                                          ______________________________________                                                                      BORIC                                                                          ANHYDRIDE                                         SOLVENT    ADDED ACID AMOUNT SOLUBILITY                                        ______________________________________                                         Trimethyl borate                                                                          +5% paratoluene   24%                                                           sulfonic acid                                                      Trimethyl borate                                                                          +20% paratoluene  40%                                                           sulfonic acid                                                      Trimethyl borate                                                                          +40% paratoluene  46%                                                           sulfonic acid                                                      Trimethyl borate                                                                          +60% paratoluene  60%                                                           sulfonic acid                                                      ______________________________________                                                            ADDED     BORIC                                                                ACID      ANHYDRIDE                                         SOLVENT            AMOUNT    SOLUBILITY                                        ______________________________________                                         Mixture       Trimethyl      +5%     16.50%                                                  borate    70%  sulfuric                                          (in weight)   Methanol  30%  acid                                              Mixture       Trimethyl      +20%    37.00%                                                  borate    70%  sulfuric                                          (in weight)   Methanol  30%  acid                                              Mixture       Trimethyl      +40%    48.00%                                                  borate    70%  sulfuric                                          (in weight)   Methanol  30%  acid                                              Mixture       Trimethyl      +60%    60.00%                                                  borate    70%  sulfuric                                          (in weight)   Methanol  30%  acid                                              ______________________________________                                    

    ______________________________________                                                   ADDED         BORIC ANHYDRIDE                                        COMPOUND  ACID AMOUNT   SOLUBILITY                                             ______________________________________                                         Methylal   +5% paratoluene                                                                             26%                                                              sulfonic acid                                                        "         +20% paratoluene                                                                             30%                                                              sulfonic acid                                                        "         +30% paratoluene                                                                             38%                                                              sulfonic acid                                                        "         +60% paratoluene                                                                             60%                                                              sulfonic acid                                                        ______________________________________                                    

EXAMPLE 3

Example 2 is repeated by using mixtures of solvents.

    ______________________________________                                                                    BORIC                                                            ADDED         ANHYDRIDE                                           COMPOUND     ACID AMOUNT   SOLUBILITY                                          ______________________________________                                         Trimethyl borate                                                                             5 parts paratoluene                                                                         43%                                                 (100 parts)  sulfonic acid                                                     Methanol: 30 parts                                                             Trimethyl borate                                                                            30 parts paratoluene                                                                         47%                                                 (100 parts)  sulfonic acid                                                     Ethanol: 30 parts                                                              Trimethyl borate                                                                            30 parts paratoluene                                                                         48%                                                 (100 parts)  sulfonic acid                                                     Isopropanol: 30 parts                                                          Trimethyl borate                                                                            30 parts paratoluene                                                                         58%                                                 (100 parts)  sulfonic acid                                                     Butanol: 30 parts                                                              ______________________________________                                    

EXAMPLE 4

Solutions were prepared by adding with stirring at room temperature powdery boric anhydride to a solution of 98% sulfuric acid solution or aromatic sulfonic acid in a solvent.

Table 3 gives the composition of the obtained solutions.

EXAMPLE 5

Use of the solutions obtained according to the present invention.

Formo-phenolic resols were obtained by condensing formol with phenol in the presence of a sodium hydroxide solution, then by neutralisation of the obtained product up to pH 7, and drying under vacuum until desired viscosity was reached.

Resol R₁ was used as it was.

Resol R₂ was diluted with methanol (5 parts per 100 parts of resol); the obtained product had a viscosity equal to 8 poises at 20° C.; it was named R'₂.

Resol R₃ was diluted with dipropylene--glycol (12 parts per 100 parts of resol, the obtained product had a viscosity equal to 15 poises at 20° C.: the obtained product was named R'₃.

In table 4, the dried extract which is given had been obtained by drying 4 g of resol for 3 hours at 140° C.

The obtained resols were mixed with the hardening solutions described in example 4. The mixture was achieved at 25° C.: the pot life is given at this temperature.

The obtained results are given in table 5.

                                      TABLE 3                                      __________________________________________________________________________     Solutions                                                                      Compounds                                                                             S.sub.1                                                                           S.sub.2                                                                           S.sub.3                                                                           S.sub.4                                                                           S.sub.5                                                                           S.sub.6                                                                           S.sub.7                                                                           S.sub.8                                                                           S.sub.9                                                                           S.sub.10                                                                          S.sub.11                                                                          S.sub.12                                                                          S.sub.13                                                                          S.sub.14                                                                          S.sub.15                                                                          S.sub.16                   __________________________________________________________________________     B(OCH.sub.3).sub.3                                                                    45.4                                                                              34.7                                                                              40.3                                                                              47.6                                                                              47.1                                                                              67.2                                                                              55.6                                                                              10.9                                                                              34.1                                                                              -- -- -- -- -- -- --                         CH.sub.2 (OCH.sub.3).sub.2                                                            -- -- -- -- -- -- -- -- -- 40.8                                                                              50 50 43.5                                                                              55.9                                                                              43.2                                                                              --                         CH.sub.3 OH                                                                           -- -- -- -- -- -- -- -- 16.7                                                                              -- -- -- -- -- -- 47                         H.sub.2 SO.sub.4                                                                      -- -- -- -- -- -- -- -- -- -- -- -- -- 17.9                                                                               5.4                                                                              --                         ATS*   27.3                                                                              48.6                                                                              40.3                                                                              33.3                                                                              29.4                                                                              21.4                                                                              19.4                                                                              27.3                                                                              22.8                                                                              32.6                                                                              -- -- 30.4                                                                              -- 24.3                                                                              42.4                       ABS*   -- -- -- -- -- -- -- -- -- -- 30 -- -- -- -- --                         AXS*   -- -- -- -- -- -- -- -- -- -- -- 30 -- -- -- --                         H.sub.2 O.sub.3                                                                       27.3                                                                              16.7                                                                              19.4                                                                              19.1                                                                              23.5                                                                              21.4                                                                              25 31.8                                                                              26.4                                                                              26.6                                                                              20 20 26.1                                                                              26.2                                                                              27.1                                                                              10.6                       __________________________________________________________________________      *ATS: paratoluene sulfonic acid                                                *ABS: benzene sulfonic acid                                                    *AXS: xylene sulfonic acid                                                     Amounts given are in percent by weight.                                  

                                      TABLE 4                                      __________________________________________________________________________                 CONDENSATION         Dried Extract                                     Molar ratio                                                                            Temperature                                                                           Reaction time                                                                         Viscosity                                                                             percent by                                    Resol                                                                              Formol/phenol                                                                          °C.                                                                            (minutes)                                                                             20° C. Poises                                                                  weight                                        __________________________________________________________________________     R.sub.1                                                                            1.5     ebullition                                                                            45-50  25-30  72-76                                         R.sub.2                                                                            1.5     "      65-75  28     72-73                                                                          (after dilution                                                                R.sub.2 ')                                    R.sub.3                                                                            1.5     "      35     25     74                                                                             (after dilution                                                                R.sub.3 ')                                    __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________             Nature                                                                               R.sub.1                                                                           R.sub.1                                                                           R.sub.1                                                                           R.sub.2 '                                                                         R.sub.2 '                                                                         R.sub.2 '                                                                         R.sub.3 '                                                                         R.sub.3 '                                                                         R.sub.3 '                                                                         R.sub.3 '                                                                         R.sub.3 '                          Resol   amount (g)                                                                           100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                        Nature                                                                               S.sub.1                                                                           S.sub.14                                                                          S.sub.15                                                                          S.sub.1                                                                           S.sub.14                                                                          S.sub.15                                                                          S.sub.1                                                                           S.sub.1                                                                           S.sub.14                                                                          S.sub.15                                                                          S.sub.16                           Hardener                                                                       Solution                                                                               amount (g)                                                                           20 20 20 20 20 20 20 15 20 20 30                                 Pot Life                                                                       25° C. (minutes)                                                                      13 20 10 5  10 4  7  12 7  5  30                                 __________________________________________________________________________

EXAMPLE 6

By using resol R₃ and solutions S₁ -S₁₀ -S₁₃ -S₁₄ -S₁₅ and S₁₆ in place of solid B₂ O₃ laminates were prepared with glass-fiber mats by injection or projection using the processes described in U.S. Pat. No. 4,123,414. The obtained products were homogeneous and had a good aspect. 

What is claimed is:
 1. In a process for hardening formo-phenolic resols, wherein a mixture comprising a formo-phenolic resin and a hardening agent is hardened;the improvement wherein said hardening agent is a concentrated boric anhydride solution which comprises (1) at least 5 percent by weight of boric anhydride; (2) at least one solvent selected from the group consisting of mono alcohols, poly alcohols, trialkylborates and dialkyl acetals of formol; and (3) from 5 to 70 percent by weight, based on the weight of solution, of at least one acid selected from the group consisting of sulfuric acid and sulfonic acids.
 2. A process according to claim 1, wherein in said concentrated boric anhydride solution, the amount of said at least one acid is at least 10 percent by weight based on the weight of solution.
 3. A process according to claim 1, wherein in said concentrated boric anhydride solution, the amount of said at least one acid is from 15 to 50 percent by weight based on the weight of solution.
 4. A process according to claim 1, wherein said concentrated boric anhydride solution, the boric anhydride concentration is from 10 to 35 percent by weight.
 5. A process according to claim 1, wherein said concentrated boric anhydride solution comprises:10 to 35 percent by weight of boric anhydride; 15 to 50 percent by weight of acid; and 30 to 60 percent by weight of organic solvent.
 6. A process according to claim 1, wherein in said concentrated boric anhydride solution, the solvent is a mixture of trimethyl borate and methanol.
 7. A process according to claim 1, wherein in said concentrated boric anhydride solution, the solvent is a mixture of trimethyl borate and methylal.
 8. A process according to claim 1, wherein the acid is sulfuric acid.
 9. A process according to claim 1, wherein the acid is para-toluenesulfonic acid.
 10. A process according to claim 5, wherein in said concentrated boric anhydride solution the solvent is a mixture of trimethyl borate and methanol.
 11. A process according to claim 5, wherein in said concentrated boric anhydride solution the solvent is a mixture of trimethyl borate and methylal. 